EP2819199B1 - Substrat für eine organische elektronische vorrichtung - Google Patents

Substrat für eine organische elektronische vorrichtung Download PDF

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Publication number
EP2819199B1
EP2819199B1 EP13769244.8A EP13769244A EP2819199B1 EP 2819199 B1 EP2819199 B1 EP 2819199B1 EP 13769244 A EP13769244 A EP 13769244A EP 2819199 B1 EP2819199 B1 EP 2819199B1
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Prior art keywords
layer
high refractive
electrode layer
organic
binder
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English (en)
French (fr)
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EP2819199A1 (de
EP2819199A4 (de
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Min Choon Park
Yeon Keun Lee
Yong Sik Ahn
Jung Doo Kim
Sang Jun Park
Yong Nam Kim
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LG Chem Ltd
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LG Chem Ltd
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10Substrates, e.g. flexible substrates
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • H10K50/854Arrangements for extracting light from the devices comprising scattering means
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • H10K50/858Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301Details of OLEDs
    • H10K2102/331Nanoparticles used in non-emissive layers, e.g. in packaging layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Definitions

  • the present application relates to a substrate for an organic electronic device (OED) and an OED.
  • OED organic electronic device
  • An OED is a device exhibiting a function through exchange of charges between an electrode layer and an organic material.
  • the OED includes an organic light emitting diode (OLED), an organic solar cell, an organic photo conductor (OPC), and an organic transistor.
  • an OLED which is a representative OED, sequentially includes a substrate, a first electrode layer, an organic layer, and a second electrode layer.
  • the first electrode layer may be a transparent electrode layer, and the second electrode layer may be a reflective electrode layer.
  • the first electrode layer may be formed as a reflective electrode layer, and the second electrode layer may be formed as a transparent electrode layer.
  • Electrons and holes injected by the electrode layers are recombined in the emitting layer located in the organic layer, resulting in generating light.
  • the light may be emitted to the substrate in the bottom emitting device, or to the second electrode layer in the top emitting device.
  • indium tin oxide (ITO) generally used as the transparent electrode layer, the organic layer, and the substrate, which is conventionally formed of glass, have refractive indexes of approximately 2.0, 1.8, and 1.5, respectively.
  • the refractive index for example, the light generated in the emitting layer in the bottom emitting device is trapped at an interface between the organic layer and the first electrode layer or in the substrate due to a total internal reflection phenomenon, and only a very small amount of light is emitted.
  • WO2011062215A1 describes an organic electroluminescent element used for illuminating device, that has a transparent base material having a hard coat layer containing metal oxide nanoparticles provided on both surfaces of transparent resin substrate.
  • the present application is directed to providing a substrate for an OED, and an OED, both as defined in the appended claims.
  • One aspect of the present application provides an illustrative substrate for an OED, including: a base layer, and a high refractive layer.
  • the term "high refractive layer” used herein may refer to a layer having a refractive index of approximately 1.8 to 2.5.
  • the term “refractive index” used herein may refer to, unless particularly defined otherwise, a refractive index with respect to light having a wavelength of approximately 550 to 633 nm.
  • the high refractive layer may be, for example, formed on the base layer.
  • FIG. 1 shows an illustrative substrate 100 including a base layer 101 and a high refractive layer 102 formed thereon.
  • the high refractive layer may be, for example, a planarized layer.
  • planarized layer used herein may refer to a layer capable of providing a planarized surface on which an OED may be formed.
  • the planarized layer may provide a surface having a maximum height roughness of 1 or 0.5 ⁇ m or less.
  • the maximum height roughness may refer to a distance between a straight line passing the maximum point of a roughness curve and a straight line passing the minimum point thereof and parallel to a central line in the roughness curve within a cut off, which may be a value measured with respect to an arbitrary region having an area of 100 ⁇ m 2 on the planarized surface.
  • a suitable material may be used without particular limitation.
  • a transparent base layer for example, a base layer having a transmittance with respect to light in a visible region of 50% or more may be used.
  • a glass base layer or a transparent polymer base layer may be used.
  • a base layer including soda lime glass, barium/strontium-containing glass, lead glass, alumino silicate glass, borosilicate glass, barium borosilicate glass, or quartz may be used
  • a base layer including polyimide (PI), polyethylene naphthalate (PEN), polycarbonate (PC), an acryl resin, poly(ethylene terephthalate) (PET), poly(ether sulfide) (PES), or polysulfone (PS) may be used, but the present application is not limited thereto.
  • the base layer may be a TFT substrate having a drive TFT.
  • a base layer may not necessarily be a transparent base layer.
  • a reflective base layer in which a reflective layer is formed using aluminum on a surface of the base layer may be used.
  • the high refractive layer may include a binder and particles.
  • the high refractive layer may be a planarized layer providing a surface on which an OED including an electrode layer may be formed.
  • the high refractive layer may also embody excellent light extraction efficiency through interaction with a scattering layer to be described later in some cases.
  • the high refractive layer may have, for example, the same refractive index as that of an adjacent electrode layer, which may be approximately 1.8 to 2.5, 1.85 to 2.5, 1.9 to 2.2, or 2.2 to 2.5.
  • the binder included in the high refractive layer a known material may be used without particular limitation.
  • the binder for example, various organic binders, inorganic binders, and organic/inorganic binders known in the art may be used.
  • the binder one of the known materials having a refractive index of approximately 1.4, 1.45, 1.5, 1.6, 1.65 or 1.7 or more may be used.
  • the upper limit of the refractive index of the binder may be selected in the range capable of satisfying the refractive index of the high refractive layer in consideration of a refractive index of the particles blended therewith.
  • An inorganic or organic/inorganic binder having excellent thermal and chemical resistances may be used in consideration of a life span of the device or excellent resistance to a high temperature process, photolithography process or etching process, which is performed during a manufacturing process, but when necessary, an organic binder may also be used.
  • the binder may be, for example, a heat or photo curable monomeric, oligomeric, or polymeric organic material including polyimide, a caldo resin having a fluorene ring, urethane, epoxide, polyester, or acrylate, an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride, or polysiloxane, or an organic/inorganic combination material.
  • the binder may include polysiloxane, poly(amic acid) or polyimide.
  • the polysiloxane may be formed by polycondensating, for example, a condensable silane compound or siloxane oligomer, and the binder may form a matrix based on a bond (Si-O) between silicon and oxygen.
  • the binder matrix based on the bond (Si-O) between silicon and oxygen may be formed by controlling condensation conditions, or a matrix in which some of organic groups such as an alkyl group or condensable functional groups such as an alkoxy group remain may be formed.
  • the poly(amic acid) or polyimide binder may have a refractive index with respect to light having a wavelength of 633 nm of, for example, approximately 1.5, 1.6, 1.65 or 1.7 or more.
  • a high refractive poly(amic acid) or polyimide may be prepared using, for example, a monomer to which a halogen atom other than fluorine, a sulfur atom or a phosphorus atom is introduced.
  • poly(amic acid) having a part capable of binding with particles such as a carboxyl group to enhance dispersion stability of the particles may be used.
  • the poly(amic acid) may be a compound including a repeating unit of Formula 1.
  • n is a positive number.
  • the repeating unit may be optionally substituted with at least one substituent.
  • a substituent a halogen atom other than fluorine, or a functional group including a halogen atom, a sulfur atom or a phosphorus atom such as a phenyl group, a benzyl group, a naphthyl group or a thiophenyl group may be used.
  • the poly(amic acid) may be a homopolymer formed using only the repeating unit of Formula 1, or a copolymer including another unit with the repeating unit of Formula 1.
  • the kind or ratio of another repeating unit may be suitably selected in the range in which, for example, a desired refractive index, thermal resistance or light transmittance is not inhibited.
  • a repeating unit of Formula 2 may be used.
  • n is a positive number.
  • the poly(amic acid) may have a weight average molecular weight converted by standard polystyrene measured by gel permeation chromatography (GPC) of approximately 10,000 to 100,000 or 10,000 to 50,000.
  • the poly(amic acid) having the repeating unit of Formula 1 may also have light transmittance in a visible region of 80, 85, or 90% or more, and have excellent thermal resistance.
  • a high refractive binder or a lowly refractive binder may be used as the binder.
  • the terms "high refractive binder” used herein may refer to a binder having a refractive index of approximately 1.7 to 2.5 or 1.7 to 2.0, and “lowly refractive binder” may refer to a binder have a refractive index of approximately equal to or more than 1.4 to less than 1.7.
  • Various binders described above are known in the art, and a suitable binder may be selected from the above-described various kinds or other known binders.
  • the high refractive layer may include high refractive particles, for example, particles having a refractive index of, for example, more than 2.3, 2.35, 2.4, 2.5, 2.6 or 2.7 or more, as well as the binder.
  • the upper limit of the refractive index of the high refractive particles may be selected in the range capable of satisfying a desired refractive index of the light scattering layer in consideration of the refractive index of the binder blended therewith.
  • the high refractive particles may have an average diameter of, for example, approximately 1 to 100, 10 to 90, 20 to 80, 30 to 70, 30 to 60, or 30 to 50 nm.
  • a rutile titanium oxide may be used, but various particles may also be used, other than the above-described one satisfying the range of the refractive index.
  • the high refractive layer may include the particles at 300, 250, or 200 parts by weight or less with respect to 100 parts by weight of the binder.
  • the lower limit of the ratio of the particles may be, for example, 60, 80, 100, 120, 140 or 160 parts by weight or more.
  • the unit "parts by weight” used herein refers to a ratio of weights between components.
  • the high refractive particles may be included at 180, 160, 150 or 120 parts by weight, or 80 to 150, 80 to 140, 80 to 130, or 90 to 120 parts by weight with respect to 100 parts by weight of the binder.
  • the lowly refractive binder when used as a binder, the high refractive particles may be included at 180 to 200 parts by weight with respect to 100 parts by weight of the binder.
  • the high refractive layer may have more excellent physical properties.
  • the high refractive layer may further include particles having a refractive index of approximately 2.0 or more, approximately 2.0 to 2.35 or 2.0 to 2.3 (hereinafter, referred to as "second particles") along with the particles having a refractive index of more than 2.3 (hereinafter, referred to as "first particles").
  • the second particles may have an average diameter, for example, similar to that of the first particle.
  • alumina, alumino silicate, titanium oxide or zirconium oxide, for example, anatase-type titanium oxide may be used.
  • a ratio (A/B) of a weight (A) of the first particles and a weight (B) of the second particles may be, for example, approximately 0.1 to 1.5 or 0.5 to 1.0, and in the above range, the high refractive layer may exhibit suitable physical properties.
  • a thickness of the high refractive layer is not particularly limited, and may be controlled within a suitable range as needed.
  • the substrate may further include a scattering layer, for example, between the base layer and the high refractive layer.
  • FIG. 2 shows an illustrative substrate 2 further including a scattering layer 201 between a base layer 101 and a high refractive layer 102.
  • the scattering layer is a layer capable of increasing light extraction efficiency, which may be formed using known material and structure that serve to scatter incident light.
  • the scattering layer may be a layer including scattering particles.
  • FIG. 3 shows an illustrative scattering layer 300 including scattering particles 301, which is formed on a base layer 101.
  • the scattering layer 300 shown in FIG. 3 may include scattering particles 301 and a binder 302.
  • scattering particles used herein may refer to, for example, particles capable of scattering incident light since they have a refractive index different from that of a surrounding medium such as a binder for forming a scattering layer or the high refractive layer and a suitable size.
  • particles having a refractive index of, for example, approximately 1.0 to 2.0, 1.2 to 1.8, 2.1 to 3.5 or 2.2 to 3.0, and an average diameter of approximately 50 to 20,000 or 100 to 5,000 nm.
  • the scattering particles may have a spherical, oval, polygonal or amorphous shape, but the shape thereof is not particularly limited thereto.
  • the scattering particles may include, for example, an organic material such as polystyrene or a derivative thereof, an acrylic resin or a derivative thereof, a silicon resin or a derivative thereof, or a novolac resin or a derivative thereof, or an inorganic material such as silica, alumina, titanium oxide or zirconium oxide.
  • the scattering particles may include any one of the above materials, or at least two thereof, or may be formed in core/shell-type particles or hollow-type particles as needed.
  • the scattering layer may further include a binder maintaining the scattering particles.
  • a binder for example, as a material capable of maintaining the scattering particles, another adjacent material such as a material having the same refractive index as the base layer may be used.
  • suitable one may be selected from a range of binders which may be used to form the high refractive layer, and another known material may also be used when necessary.
  • the scattering layer may be, for example, a layer having an uneven structure.
  • FIG. 4 is a diagram showing that a scattering layer 401 having an uneven structure is formed on a base layer 101. When the uneven structure of the scattering layer is suitably controlled, incident light may be scattered.
  • the scattering layer having an uneven structure may be formed, for example, by coating a heat- or photo-curable material, and curing the material in contact with a mold capable of transferring a desired shape of the uneven structure during curing or performing an etching process.
  • the scattering layer may be formed by blending particles having a suitable size and shape in a binder for forming the scattering layer. In this case, the particles may not need to be particles having a scattering function, but particles having a scattering function may also be used.
  • the scattering layer may be formed by coating a material by wet coating, and performing application of heat or irradiation of light, curing of the material by a sol-gel method, deposition such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), or microembossing.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the substrate may further include an electrode layer.
  • the electrode layer may be formed on the high refractive layer.
  • a conventional hole injection or electron injection electrode layer used to manufacture an OED such as an OLED may be formed.
  • the hole injection electrode layer may be formed using a material having, for example, a relatively high work function, and when necessary, using a transparent material.
  • the hole injection electrode layer may include a metal, an alloy, an electric conductive compound having a work function of approximately 4.0 eV or more, or a mixture of at least two thereof.
  • Such a material may be a metal such as gold, CuI, ITO, indium zinc oxide (IZO), zinc tin oxide (ZTO), aluminum or indium-doped zinc oxide, magnesium indium oxide, nickel tungsten oxide, an oxide material such as ZnO, SnO 2 or In 2 O 3 , a metal nitride such as gallium nitride, a metal selenide such as zinc selenide, or a metal sulfide such as zinc sulfide.
  • a transparent hole injection electrode layer may also be formed using a stacked structure of a metal thin film such as Au, Ag, or Cu and a high refractive transparent material such as ZnS, TiO 2 or ITO.
  • the hole injection electrode layer may be formed by an arbitrary means such as deposition, sputtering, chemical deposition, or an electrochemical means. In addition, as needed, the formed electrode layer may be patterned through known photolithography or a process using a shadow mask. A thickness of the hole injection electrode layer may vary according to light transmittance or surface resistance, but may conventionally be 500 nm or in a range of 10 to 200 nm.
  • the transparent electron injection electrode layer may be formed using, for example, a transparent material having a relatively low work function, and for example, a suitable one of the materials used to form the hole injection electrode layer may be used, but the present application is not limited thereto.
  • the electron injection electrode layer may be formed using, for example, deposition or sputtering, and when necessary, may be suitably patterned.
  • the electron injection electrode layer may be formed to a suitable thickness as needed.
  • the high refractive layer or the high refractive layer and the scattering layer may have a smaller projected area than that of the electrode layer.
  • the high refractive layer may have a smaller projected area than that of the base layer.
  • projected area used herein refers to a projected area of a target recognized when the substrate is observed from above or below in a direction parallel to the normal line of a surface thereof, for example, an area of the base layer, high refractive layer, scattering layer or electrode layer.
  • the high refractive layer or scattering layer has a smaller projected area than that of the electrode layer.
  • the high refractive layer and the like may be present in various types when they have a smaller projected area than those of the base layer and the electrode layer.
  • the high refractive layer 102 or the high refractive layer 102 and the scattering layer 201 may be formed only at a part of the base layer 101 other than an edge thereof, or a part of the high refractive layer may remain at the edge of the base layer.
  • FIG. 7 is a diagram of the substrate of FIG. 5 when observed from above.
  • an area (A), that is, a projected area (A), of the electrode layer 501 recognized when the substrate is observed from above is larger than an area (B), that is, a projected area (B) of the scattering layer 102 disposed therebelow.
  • a ratio (A/B) of the projected area (A) of the electrode layer 501 and the projected area (B) of the high refractive layer 102 or the scattering layer may be, for example, 1.04, 1.06, 1.08, 1.1, or 1.15 or more.
  • the upper limit of the ratio (A/B) in projected area is not particularly limited.
  • the upper limit of the ratio (A/B) may be, for example, approximately 2.0, 1.5, 1.4, 1.3 or 1.25.
  • the electrode layer may be formed on the top of the base layer on which the high refractive layer is not formed.
  • the electrode layer may be formed in contact with the base layer, or an additional component may be further included between the electrode layer and the base layer. According to such a structure, in the embodiment of the OED, a structure in which the high refractive layer is not exposed to an external environment may be embodied.
  • the electrode layer 501 may be formed in a region including a region beyond all of peripheral regions of the scattering layer 102 when observed from above.
  • the electrode layer may be formed up to the region including the region beyond all of the peripheral regions of at least one high refractive layer, for example, the scattering layer on which an organic layer will be formed at least the top thereof.
  • a structure in which the high refractive layer and the like are not exposed to an external environment may be formed by attaching an encapsulating structure to be described later to an electrode layer below which the high refractive layer is not formed.
  • an electrode is formed to cover the high refractive layer and the like in a deposition or sputtering process for forming an electrode. In this process, when necessary, a process of removing a predetermined part of the high refractive layer may be performed.
  • the substrate may further include, for example, an intermediate layer present between the high refractive layer and the electrode layer.
  • the intermediate layer may have a larger projected area than that of the high refractive layer, and may be formed on the top of the high refractive layer and the top of the base layer which does not have the high refractive layer.
  • the intermediate layer may solve an increase in resistance of the electrode layer by reducing a step difference on the boundary between the electrode layer on the high refractive layer and the electrode layer on the base layer, which is formed by the high refractive layer having a smaller projected area than that of the electrode layer as described above.
  • the intermediate layer when a material having a barrier property, that is, a low moisture or vapor penetration rate is used, a structure in which the high refractive layer is not exposed to an external environment may be more effectively embodied.
  • the intermediate layer may be a layer having an absolute value of a difference in refractive index between the intermediate layer and the electrode layer of, for example, approximately 1, 0.7, 0.5, or 0.3 or less.
  • a material for forming the intermediate layer may be a material having a relationship of the refractive index with the electrode layer, and a barrier property when necessary.
  • TiOx titanium oxide
  • SiOx silicon oxide
  • AlOx aluminum oxide
  • Ta 2 O 3 titanium oxide
  • Ti 3 O 3 titanium oxide
  • TiO, ZrO 2 , Nb 2 O 3 another metal oxide
  • CeO 2 zirconium oxide
  • ZnS or ZnO zirconium oxide
  • oxynitride a material that various materials, for example, titanium oxide (TiOx) such as SiON or TiO 2 , silicon oxide (SiOx) such as SiO 2 , aluminum oxide (AlOx) such as Al 2 O 3 , another metal oxide such as Ta 2 O 3 , Ti 3 O 3 , TiO, ZrO 2 , Nb 2 O 3 , CeO 2 , ZnS or ZnO, or oxynitride
  • the intermediate layer may be formed by a known method such as deposition such as PVD, CVD or ALD, sputtering, or wet coating.
  • a thickness of the intermediate layer may be, but is not particularly limited to
  • the illustrative organic electronic system of the present application may include the substrate for an OED described above, and an OED formed on the substrate, for example, a high refractive layer of the substrate.
  • the OED may include, for example, a first electrode layer, an organic layer and a second electrode layer, which are sequentially formed on the high refractive layer.
  • the OED may be an OLED.
  • the OED may have, for example, a structure in which an organic layer including at least an emitting layer is intermediated between a hole injection electrode layer and an electron injection electrode layer.
  • the hole injection electrode layer or the electron injection electrode layer may be an electrode layer on the high refractive layer of the substrate described above.
  • the organic layer present between the electron and hole injection electrode layers may include at least one emitting layer.
  • the organic layer may include multiple, that is, at least two emitting layers.
  • the emitting layers may have a structure split by an inter-electrode having a charge generating characteristic or a charge generating layer (CGL), but the present application is not limited thereto.
  • the emitting layer may be formed using, for example, various fluorescent or phosphorescent organic materials known in the art.
  • An example of the material capable of being in the emitting layer may be, but is not limited to, a fluorescent material such as an Alq-based material such as tris(4-methyl-8-quinolinolate)aluminum(III) (Alg3), 4-MAlq3 or Gaq3; a cyclopenadiene derivative such as C-545T(C 26 H 26 N 2 O 2 S), DSA-amine, TBSA, BTP, PAP-NPA, spiro-FPA, Ph 3 Si (PhTDAOXD), 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene (PPCP), 4,4'-bis(2,2'-diphenylyinyl)-1,1'-biphenyl (DPVBi), distyryl benzene or a derivative thereof, or 4-(dicyanomethylene)-2-tert-butyl-6
  • the emitting layer may include the material as a host, and a host-dopant system including perylene, distyrylbiphenyl, DPT, quinacridone, rubrene, BTX, ABTX or DCJTB as a dopant.
  • a host-dopant system including perylene, distyrylbiphenyl, DPT, quinacridone, rubrene, BTX, ABTX or DCJTB as a dopant.
  • the emitting layer may also be formed by employing one suitable type selected from electron accepting organic compounds and electron donating organic compounds exhibiting excellent emitting characteristics, which will be described later.
  • the organic layer may be formed in various structures further including various functional layers known in the art, as long as it includes the emitting layer.
  • a layer capable of being included in the organic layer an electron injection layer, a hole blocking layer, an electron transport layer, a hole transport layer or a hole injection layer may be used.
  • the electron injection layer or electron transport layer may be formed using, for example, an electron accepting organic compound.
  • an electron accepting organic compound a known optional compound may be used without particular limitation.
  • an organic compound a polycyclic compound such as p-terphenyl or quaterphenyl or a derivative thereof; a polycyclic hydrocarbon compound such as naphthalene, tetracene, pyrene, coronene, chrysene, anthracene, diphenylanthracene, naphthacene, or phenanthrene or a derivative thereof; or a heterocyclic compound such as phenanthroline, bathophenanthroline, phenanthridine, acridine, quinoline, quinoxaline, or phenazine or a derivative thereof.
  • a metal complex having at least one of metal chelated oxinoid compounds such as 8-quinolatos including tris(8-quinolinolato)aluminum, bis(8-quinolinolato)magnesium, bis[benzo(f)-8-quinolinolato]zinc, bis(2-methyl-8-quinolinolato)aluminum, tris(8-quinolinolato)indium, tris(5-methyl-8-quinolinolato)aluminum, 8-quinolinolatolithium, tris(5-chloro-8-quinolinolato)gallium, bis(5-chloro-8-quinolinolato)calcium and derivatives thereof as a coordinator; an oxadiazole compound disclosed in a patent publication such as Japanese Patent Application Laid-Open No.
  • a diolefin derivative disclosed in a patent publication such as Japanese Patent Application Laid-Open No. 1994-100857 or Japanese Patent Application Laid-Open No. 1994-207170 ;
  • a fluorescent brightening agent such as a benzooxazole compound, a benzothiazole compound or a benzoimidazole compound;
  • a distyrylbenzene compound such as 1,4-bis(2-methylstyryl)benzene, 1,4-bis(3-methylstyryl)benzene, 1,4-bis(4-methylstyryl)benzene, distyrylbenzene, 1,4-bis(2-ethylstyryl)benzyl, 1,4-bis(3-ethylstyryl)benzene, 1,4-bis(2-methylstyryl)-2-methylbenzene or 1,4-bis(2-methylstyryl)-2-ethylbenzene; a distyrylpyrazine compound such as 2,
  • a tetraphenyl butadiene compound disclosed in a patent publication such as Japanese Patent Application Laid-Open No. 1992-96990 ; an organic trifunctional compound disclosed in a patent publication such as Japanese Patent Application Laid-Open No. 1991-296595 ; a coumarin derivative disclosed in a patent publication such as Japanese Patent Application Laid-Open No. 1990-191694 ; a perylene derivative disclosed in a patent publication such as Japanese Patent Application Laid-Open No. 1990-196885 ; a naphthalene derivative disclosed in a patent publication such as Japanese Patent Application Laid-Open No.
  • a phthaloperynone derivative disclosed in a patent publication such as Japanese Patent Application Laid-Open No. 1990-289676 or Japanese Patent Application Laid-Open No. 1990-88689 ; or a styryl amine derivative disclosed in a patent publication such as Japanese Patent Application Laid-Open No. 1990-250292 may be used as an electron accepting organic compound included in a lowly refractive layer.
  • the electron injection layer may be formed using, for example, a material such as LiF or CsF.
  • the hole blocking layer may be a layer capable of enhancing a life span and efficiency of the device by preventing approach of holes injected from a hole injection electrode to an electron injection electrode through the emitting layer, and may be formed in a suitable part between the emitting layer and the electron injection electrode using a known material when necessary.
  • the hole injection layer or hole transport layer may include, for example, an electron donating organic compound.
  • an electron donating organic compound N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4' -diaminobiphenyl, 2,2-bis(4-di-p-tollylaminophenyl)propane, N,N,N',N'-tetra-p-tollyl-4,4'-diaminobiphenyl, bis(4-di-p-tollylaminophenyl)phenylmethane, N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N' ,N' -tetraphenyl-4,4' -diaminodiphenylether
  • the hole injection layer or hole transport layer may be formed by dispersing the organic compound in a polymer, or using a polymer derived from the organic compound.
  • a ⁇ -conjugated polymer such as polyparaphenylenevinylene and a derivative thereof
  • a hole transport non-conjugated polymer such as poly(N-vinylcarbazole) or a ⁇ -conjugated polymer of polysilane may also be used.
  • the hole injection layer may be formed using an electrically-conductive polymer such as a metal phthalocyanine such as copper phthalocyanine or a non-metal phthalocyanine, a carbon layer and polyaniline, or may be formed by reaction with a Lewis acid using the aryl amine compound as an oxidizing agent.
  • an electrically-conductive polymer such as a metal phthalocyanine such as copper phthalocyanine or a non-metal phthalocyanine, a carbon layer and polyaniline, or may be formed by reaction with a Lewis acid using the aryl amine compound as an oxidizing agent.
  • the OLED may be formed in a type of (1) a hole injection electrode layer/an organic emitting layer/an electron injection electrode layer; (2) a hole injection electrode layer/a hole injection layer/an organic emitting layer/an electron injection electrode layer; (3) a hole injection electrode layer/an organic emitting layer/an electron injection layer/an electron injection electrode layer; (4) a hole injection electrode layer/a hole injection layer/an organic emitting layer/an electron injection layer/an electron injection electrode layer; (5) a hole injection electrode layer/an organic semiconductor layer/an organic emitting layer/an electron injection electrode layer; (6) a hole injection electrode layer/an organic semiconductor layer/an electron barrier layer/an organic emitting layer/an electron injection electrode layer; (7) a hole injection electrode layer/an organic semiconductor layer/an organic emitting layer/an adhesion-improving layer/an electron injection electrode layer; (8) a hole injection electrode layer/a hole injection layer/a hole transport layer/an organic emitting layer/an electron injection electrode layer; (9) a hole injection electrode layer/an insulator layer/an insulator
  • a hole or electron injection electrode layer and an organic layer for example, an emitting layer, an electron injection or transport layer, or a hole injection or transport layer and methods of forming the same are known in the art, and all of the above-described methods may be applied to manufacture the organic electronic system.
  • the organic electronic system may further include an encapsulating structure.
  • the encapsulating structure may be a protective structure for preventing inflow of an external material such as moisture or oxygen to the organic layer of the organic electronic system.
  • the encapsulating structure may be, for example, a can such as a glass can or a metal can, or a film covering an entire surface of the organic layer.
  • FIG. 8 shows that an organic layer 701 and a second electrode layer 702 formed on a substrate including a base layer 101, a high refractive layer 102 and a first electrode layer 501, which are sequentially formed, are protected by an illustrative encapsulating structure 703 formed in a can structure such as a glass can or a metal can.
  • the encapsulating structure 703 may be attached by an adhesive.
  • the encapsulating structure 703 may be adhered to the substrate, for example, the electrode layer 501 below which the high refractive layer 102 is not present.
  • the encapsulating structure 703 as shown in FIG. 8 may be attached to an end of the substrate by an adhesive. According to such a method, a protecting effect by the encapsulating structure may be optimized.
  • the encapsulating structure may be, for example, a film coating entire surfaces of an organic layer and a second electrode layer.
  • FIG. 9 shows an illustrative film-type encapsulating structure 703 covering entire surfaces of an organic layer 701 and a second electrode layer 702.
  • the film-type encapsulating structure 703 may cover the entire surfaces of the organic layer 701 and the second electrode layer 702, and have a structure in which the substrate including the base layer 101, the high refractive layer 102 and the electrode layer 501 is adhered to a second substrate 801 disposed thereon.
  • the second substrate 801 a glass substrate, a metal substrate, a polymer film or a barrier layer may be used as the second substrate 801, a glass substrate, a metal substrate, a polymer film or a barrier layer may be used.
  • the film-type encapsulating structure may be formed by, for example, coating a liquid material cured by heat or UV irradiation such as an epoxy resin and curing the liquid material, or laminating the substrate with the upper substrate using an adhesive sheet previously manufactured in a film type using the epoxy resin.
  • the encapsulating structure may include a water adsorbent or getter such as a metal oxide such as calcium oxide or beryllium oxide, a metal halide such as calcium oxide, or phosphorus pentoxide, when necessary.
  • a water adsorbent or getter such as a metal oxide such as calcium oxide or beryllium oxide, a metal halide such as calcium oxide, or phosphorus pentoxide, when necessary.
  • the water adsorbent or getter may be included in the film-type encapsulating structure, or present at a predetermined position of a can-type encapsulating structure.
  • the encapsulating structure may further include a barrier film or a conductive film.
  • the encapsulating structure may be attached to, for example, the top of the first electrode layer 501 below which the high refractive layer 102 is not formed.
  • a sealing structure in which the high refractive layer is not exposed to an external environment may be embodied.
  • the sealing structure may refer to, for example, a state in which the entire surface of the high refractive layer is not exposed to an external environment by being surrounded by the base layer, the electrode layer and/or the encapsulating structure, or by being surrounded by the sealing structure formed to include the base layer, the electrode layer and/or the encapsulating structure.
  • the sealing structure may be formed to only include the base layer, the electrode layer and/or the encapsulating structure, or to include the base layer, the electrode layer, the encapsulating structure, and also another component, for example, an auxiliary electrode as long as the high refractive layer is not exposed to an external environment.
  • another component may be present at a part in which the base layer 101 is in contact with the electrode layer 501 or the electrode 501 is in contact with the encapsulating structure 703 or another position.
  • an organic, inorganic or organic/inorganic combination material having a low water permeability, an insulating layer or an auxiliary electrode may be used as the another component.
  • Still another aspect of the present application provides a use of the organic electronic system, for example, the organic light emitting system.
  • the organic light emitting system may be effectively applied to a backlight of a liquid crystal display (LCD), lightings, sensors, printers, a light source of a copy machine, a light source for an automobile gauge, a signal light, a pilot lamp, a display device, a light source for a planar emitting device, a display, decorations or other kinds of lights.
  • the present application relates to a lighting device including the OLED.
  • other components constituting the device or a method of constituting the device is not particularly limited, but all of optional materials or methods known in the related art may be employed as long as these are used in the OLED.
  • a substrate for an OED such as an OLED
  • a substrate capable of providing an organic electronic system having excellent performance and reliability can be provided.
  • a coating solution for a light scattering layer was prepared by blending and sufficiently dispersing scattering particles (titanium oxide particles) having an average diameter of approximately 200 nm in a sol-gel coating solution including tetramethoxy silane as a condensable silane.
  • a light scattering layer was formed to have a thickness of approximately 300 nm by coating the coating solution on a glass substrate, and performing a sol-gel reaction at 200 °C for approximately 30 minutes.
  • the light scattering layer and the planarized layer were partially removed by radiating a laser to the formed layer such that positions of the remaining light scattering layer and the planarized layer corresponded to an emitting region of an organic layer to be subsequently formed.
  • a hole injection electrode layer including ITO was formed on the entire surface of the glass substrate to have a predetermined thickness by a known sputtering method.
  • an organic layer capable of emitting white light was formed on the ITO layer by known material and method, and an aluminum (Al) electrode was also formed on the top of the organic layer by a vacuum deposition method as an electron injection reflective electrode, thereby manufacturing a device.
  • External quantum efficiency (light extraction efficiency) measured with respect to the manufactured device was approximately 51.4%.
  • External quantum efficiency (light extraction efficiency) measured with respect to the manufactured device in the same manner as in Example 1 was approximately 54.5%.
  • External quantum efficiency (light extraction efficiency) measured with respect to the manufactured device in the same manner as in Example 1 was approximately 47.4%.
  • FIGS. 10 and 11 show emitting states of the organic electronic systems according to Examples 1 and 2, respectively, and FIG 12 shows an emitting state of the organic electronic system according to Comparative Example 1.
  • Comparative Example 1 from the drawings, many dot spots were observed, and thus it was confirmed that reliability of the device was considerably degraded.

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  • General Physics & Mathematics (AREA)
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  • Dispersion Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Claims (13)

  1. Substrat (100, 200, 500, 600) für eine organisch-elektronische Vorrichtung, umfassend:
    eine Basisschicht (101);
    eine auf der Basisschicht vorgesehene hochbrechende Schicht (102), die ein Bindemittel mit einem Brechungsindex von 1,4 oder mehr umfasst und Partikel mit einem Brechungsindex von mehr als 2,3 in einem Gehalt von 60 bis 300 Gewichtsteilen relativ zu 100 Gewichtsteilen des Bindemittels umfasst, und
    eine Brechungsschicht (201, 300, 401) zwischen und in Kontakt mit der Basisschicht und der hochbrechenden Schicht,
    wobei die hochbrechende Schicht einen Brechungsindex von 1,8 bis 2,5 aufweist.
  2. Substrat gemäß Anspruch 1, wobei die maximale Höhenrauigkeit einer Fläche der hochbrechenden Schicht, die einer mit der Basisschicht in Kontakt stehenden Fläche gegenübersteht, 1 µm oder weniger beträgt.
  3. Substrat gemäß Anspruch 1, wobei ein Brechungsindex des Bindemittels 1,4 oder mehr und weniger als 1,7 beträgt,
    wobei die hochbrechende Schicht die Partikel in einem Gehalt von 180 bis 200 Gewichtsteilen relativ zu 100 Gewichtsteilen des Bindemittels umfasst.
  4. Substrat gemäß Anspruch 1, wobei das Bindemittel einen Brechungsindex im Bereich von 1,7 bis 2,0 aufweist,
    wobei die hochbrechende Schicht die Partikel in einem Gehalt von 80 bis 150 Gewichtsteilen relativ zu 100 Gewichtsteilen des Bindemittels umfasst.
  5. Substrat gemäß Anspruch 1, wobei das Bindemittel Polysiloxan, Poly(amidsäure) oder Polyimid ist.
  6. Substrat gemäß Anspruch 1, wobei die Partikel einen durchschnittlichen Durchmesser im Bereich von 1 nm bis 50 nm aufweisen.
  7. Substrat gemäß Anspruch 1, wobei die Partikel Rutil-Titanoxid sind.
  8. Substrat gemäß Anspruch 1, wobei die hochbrechende Schicht weiterhin Partikel mit einem Brechungsindex von 2,0 bis 2,3 umfasst.
  9. Substrat gemäß Anspruch 8, wobei die Partikel mit einem Brechungsindex von 2,0 bis 2,3 Anatas-Titanoxid sind.
  10. Substrat gemäß Anspruch 8, wobei das Verhältnis (A/B) worin (A) das Gewicht des Partikels mit einem Brechungsindex von mehr als 2,3 ist und (B) das Gewicht des Partikels mit einem Brechungsindex von 2,0 bis 2,3 ist, von 0,5 bis 1,5 beträgt.
  11. Substrat gemäß Anspruch 1, weiterhin umfassend: eine auf der hochbrechenden Schicht gebildete Elektrodenschicht (501),
    wobei die hochbrechende Schicht eine kleinere Projektionsfläche als die der Elektrodenschicht aufweist und die Elektrodenschicht gebildet ist sowohl auf der hochbrechenden Schicht als auch auf der Basisschicht, unterhalb derer die hochbrechende Schicht nicht gebildet ist.
  12. Organisch-elektronische Vorrichtung, umfassend:
    Das Substrat gemäß Anspruch 1; und
    Eine erste Elektrodenschicht (501); eine organische Schicht (701), umfassend eine emittierende Schicht; und eine zweite Elektrodenschicht (702); die sequentiell auf dem Substrat gebildet sind,
    wobei die organische Schicht eine emittierende Schicht umfasst, und
    wobei eine Projektionsfläche einer hochbrechenden Schicht des Substrats kleiner als die der ersten Elektrodenschicht ist, wenn die erste Elektrodenschicht sowohl auf der hochbrechenden Schicht als auch auf der Basisschicht, die nicht die hochbrechende Schicht aufweist, gebildet ist.
  13. Leuchtmittel, umfassend die organisch-elektronische Vorrichtung gemäß Anspruch 12.
EP13769244.8A 2012-03-30 2013-04-01 Substrat für eine organische elektronische vorrichtung Active EP2819199B1 (de)

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US9583721B2 (en) 2017-02-28
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EP2819199A4 (de) 2015-12-23

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